CN114014297B - Carbon nanotube ring and preparation method thereof - Google Patents

Carbon nanotube ring and preparation method thereof Download PDF

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CN114014297B
CN114014297B CN202111315430.9A CN202111315430A CN114014297B CN 114014297 B CN114014297 B CN 114014297B CN 202111315430 A CN202111315430 A CN 202111315430A CN 114014297 B CN114014297 B CN 114014297B
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carbon nanotube
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魏飞
江雅馨
朱振兴
高俊
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Tsinghua University
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Abstract

The invention discloses a carbon nanotube ring and a preparation method thereof, belonging to the technical field of nano material preparation. The carbon nano tube ring is formed by coiling a single carbon nano tube with the diameter of 0.4-10nm, the number of tube walls of 1-5, the length of more than 10 mu m and a perfect structure, and the average curvature radius is distributed between 50nm and 2 mu m. The preparation method leads in an external field through the end of the carbon nano tube generating reactor, so that the carbon nano tubes are separated under the induction of the external field; and spraying fog drops in the range of an external field, and collecting through a substrate to obtain the carbon nanotube ring. The preparation method realizes the lossless separation of the carbon nanotubes with different chiral structures while in-situ preparation, and obtains the carbon nanotubes with high purity, high density and specific topological structure. The size of the fog drops is changed to realize the accurate regulation and control of the ring size of the carbon nano tube from a nanometer level to a micron level, and a better platform is provided for the visualization and the operation of a single carbon nano tube.

Description

Carbon nanotube ring and preparation method thereof
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a carbon nano tube ring and a preparation method thereof.
Background
The carbon nanotube is a special carbon nanomaterial with a hollow tubular structure and a high length-diameter ratio, and can be regarded as formed by curling a single-layer graphene along a certain direction, and the optical rotation and chiral parameters of the carbon nanotube are determined by the curling direction. Based on the unique hollow tubular structure and excellent mechanical, thermal, electrical, magnetic and optical properties of the carbon nano tube, the carbon nano tube has wide application prospects in the fields of nano electrical elements, field emission devices, sensors, photoelectric detection, electrochemical energy storage, composite materials and the like in recent years.
The structure determines the properties. Since the discovery of carbon nanotubes, researchers have prepared carbon nanotubes in a variety of different morphologies, such as carbon nanotube arrays, serpentine carbon nanotubes, helical carbon nanotubes, and carbon nanotube coils. The carbon nanotube ring is also a special structure of carbon nanotubes, and was first prepared by Jie Liu of rice university using laser evaporation. Compared with other carbon nanotubes with special structures, the ring structure of the carbon nanotube ring has unique advantages. Compared with the carbon nanotube array, the carbon nanotube ring is formed by coiling the carbon nanotubes, so that the density of the carbon nanotubes can be greatly improved; compared with snake-shaped and spiral carbon nanotubes, the special annular structure of the carbon nanotube ring makes the carbon nanotube ring have potential application in the field of electromagnetic induction; the highly ordered structure of the carbon nanotube rings will bring about a greater gain effect than the carbon nanotube coils.
Researchers have therefore been working on exploring new carbon nanotube ring fabrication strategies. Overall, the preparation strategies for carbon nanotube rings can be divided into two categories: one is to make the carbon nanotube produce the structural defect through the high-speed shearing process or modified method of catalyst, the topological defect of the non-six-membered ring will change the curvature of the carbon nanotube and then coil and form the ring, for example, the eddy current apparatus developed by Alhardi et al can make the carbon nanotube ring with the average ring diameter of about 0.3 μm under the condition of continuous flow, but the defect will cause the transformation of the chiral structure of the carbon nanotube, the carbon nanotube ring prepared has low chiral purity; the other is to induce the ring formation of the carbon nanotube by a template, for example, vossmeyer et al adopts a template method to assist the evaporation method to prepare the carbon nanotube ring with the ring diameter of 0.1-5 μm, wang et al uses Pickering emulsion which is a soft template agent to lead the carbon nanotube to generate the self-assembly behavior at the phase interface to synthesize the carbon nanotube ring with the ring diameter of about 0.2 μm, and the carbon nanotube ring prepared by the template method has the problems of difficult template removal and damage to the perfect structure of the carbon nanotube in the removal process. In addition, the carbon nanotube rings prepared by the two methods are usually formed by winding carbon nanotubes with different chiralities after being formed, the carbon nanotube rings prepared by the methods are mixtures of carbon nanotubes with different chiralities, and the defects of non-six-membered ring structures are introduced in the preparation or template removal processes, so that the research on the properties and the application of the carbon nanotubes is directly limited.
The large-scale preparation of the single chiral carbon nanotube without structural defects is a premise and a basis for revealing the intrinsic physical characteristics of the carbon nanotube and developing the application of the carbon nanotube. However, the properties of carbon nanotubes strongly depend on the diameter and chirality, and the structural control of growth and separation of chiral structures of carbon nanotubes are challenging at present, so how to develop a carbon nanotube material with perfect structure and consistent chirality is the main direction in the prior art.
On the other hand, the diameter of a single carbon nanotube is in a nanometer level, the appearance characterization and operation of the single carbon nanotube depend on high-grade instruments such as an electron microscope or an atomic force microscope for a long time, and the single carbon nanotube consumes long time and has low efficiency. In recent years, researchers have made individual carbon nanotubes clearly positioned and manipulated under an optical microscope by depositing nanoparticles such as anthracene, sulfur, titanium dioxide, etc. on the surface of the carbon nanotubes, which have a strong scattering ability for visible light. However, the method has the defects that partial nano particles are difficult to remove, and the surface of the carbon nano tube is polluted, so that the subsequent application of the carbon nano tube is influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a carbon nanotube ring, which is formed by overlapping and coiling carbon nanotubes with the single diameter of 0.4-10nm, the number of tube walls of 1-5, the length of more than 10 mu m and a perfect structure, wherein the average curvature radius of the carbon nanotube ring is 50nm-2 mu m.
The carbon nanotube ring has a single chiral structure, the chiral selectivity reaches 100%, and the purity is 100%.
The diameter of the single carbon nano tube is 0.7-4nm, and the length is more than 30 mu m.
The carbon nanotube ring is one or more than two rings formed by overlapping and coiling a single carbon nanotube.
The preparation method of the carbon nanotube ring comprises the following steps:
a) Sublimating the catalyst in an inert environment, and then heating and reacting the catalyst with mixed reaction gas of a carbon source and carrier gas to prepare a carbon nano tube;
b) The carbon nano tube is carried to the gas outlet of the reactor by carrier gas, and an external field is applied to the gas outlet end, so that the carbon nano tube is separated under the induction of external field force;
c) And spraying fog drops into an external field area at the gas outlet end of the reactor, and collecting the fog drops through the substrate to obtain the carbon nanotube ring.
The method separates the floated tube bundle into single carbon nanotubes by introducing an external field at the end of the reactor. Meanwhile, spraying fog drops in the range of the external field, and utilizing the surface tension of the fog drops to coil the single carbon nano tube floating under the induction of the external field to obtain a carbon nano tube ring which is formed by coiling the single carbon nano tube and has consistent chirality. The invention adopts the carbon nano tube to prepare the homochiral carbon nano tube ring, does not need an organic template reagent, further omits the operations of removing the independent template reagent by subsequent etching and the like, and realizes the synchronous preparation and separation of the carbon nano tube ring.
The preparation method of the carbon nano tube comprises the following steps:
one or more of inert gas or nitrogen is used as carrier gas, before reaction, the carrier gas is firstly introduced to keep the inert environment in the reaction device, and impurity gas is removed;
preparing a carbon nano tube by adopting a reaction device with the length of a constant-temperature area being more than 1 m; preferably, the length of the constant-temperature area is more than 2 m; more preferably, it is 2 to 10m. The reaction device comprises a high-temperature tube furnace.
The method specifically comprises the following steps:
1) Mixing a catalyst precursor and a growth promoter in a container, and then placing the container in a low-temperature region at the upstream of the gas of the reaction device;
2) Introducing carrier gas to keep an inert environment in the reaction device, removing impurity gas, heating a constant temperature area at the downstream of the reaction device, adjusting the flow of the carrier gas, and introducing a carbon source; the carbon source comprises hydrocarbon gas, preferably any one of methane, ethylene and acetylene; the flow rate of the carbon source is 1-20sccm; the flow rate of the carrier gas is 800-1500 sccm; heating the constant temperature area to 800-1200 ℃, wherein the temperature fluctuation range of the constant temperature area is +/-1 ℃;
3) And heating the low-temperature area to the sublimation temperature of 60-90 ℃, so that the catalyst precursor and the growth promoter are decomposed to form catalyst particles, then the catalyst particles enter the constant-temperature area of the reaction device along with the carrier gas to react to obtain the carbon nano tubes, and the generated carbon nano tubes flow out of the constant-temperature area along with the carrier gas in an aerogel form and are collected at an outlet.
The carbon nanotubes with different wall numbers are obtained by changing the temperature of the catalyst precursor and the flow of the carrier gas.
The catalyst precursor comprises one or more of volatile metal organic compounds, preferably comprises one or more of ferrocene, nickelocene and cobaltocene;
the growth promoter comprises one or more of sulfur-containing substances, preferably one or more of sulfur powder and sulfur-containing organic substances;
more preferably, the catalyst precursor and growth promoter are ferrocene and sublimed sulfur in a molar ratio of from 20.
In the step B), the external field is any one of an electric field, a magnetic field and an optical field;
the external field is a high-voltage electric field, an electrode plate connected with a direct-current power supply is vertically arranged at the air outlet end of the reactor, and the strength of the electric field is jointly controlled by the output voltage of the high-voltage direct-current power supply and the position of the electrode plate. The electrode plate can move dynamically, and the distance from the outlet of the reactor to the electrode plate and the magnitude of output voltage are adjusted to control the field intensity from the outlet of the reactor to the electrode plate, namely the field intensity in a droplet region is between 50 and 200 kV/m;
preferably, the field intensity is controlled between 60 kV/m and 150 kV/m;
more preferably, the field intensity is controlled between 70 and 130 kV/m; the voltage-variable resistor specifically comprises 80kV/m, 100kV/m and 120kV/m.
Within the field intensity range, the mist quantity is controlled to be 200-300mL/h to obtain a monocyclic carbon nanotube ring; the fog amount is less than 200mL/h, and a polycyclic carbon nanotube ring is obtained.
In the step C), the fog drops are one of water drops, oil drops, ethanol drops and acetone drops.
The average curvature radius distribution of the carbon nano tube ring is adjusted by changing the diameter of the color spot formed by the fog drops, the diameter of the color spot is between 0.1 and 2mm, and the average curvature radius distribution of the corresponding carbon nano tube ring is between 50nm and 2 mu m.
Controlling the diameter of a color spot formed by the fog drops to be 0.17mm, and obtaining the average curvature radius distribution of the carbon nano tube ring to be 300-500nm;
controlling the diameter of the color spot formed by the fog drops to be 0.5mm, controlling the average curvature radius distribution of the carbon nano tube ring to be 400-700nm, controlling the diameter of the color spot formed by the fog drops to be 1mm, and controlling the average curvature radius distribution of the carbon nano tube ring to be 0.8-1.1 mu m.
In step C), the substrate comprises a solid substrate and a liquid substrate; the solid substrate comprises any one of a silicon wafer, quartz, gold foil and copper foil; the liquid substrate comprises any one of water, ethanol, ethylene glycol and polyethylene glycol.
After the carbon nanotube ring is overlapped and coiled by a single carbon nanotube, the scattering cross section is multiplied, and the carbon nanotube ring is used for optical measurement and characterization of the single carbon nanotube.
The invention has the beneficial effects that:
1. according to the invention, through the rigidity strength of the ultra-long carbon nano tube, a single carbon nano tube is enabled to take the fog drops which are not required to be removed as a coiling center by using a physical method, so that a carbon nano tube ring which is uniformly coiled in an overlapping way is obtained, the step that a carbon nano ring forming template is removed by subsequent single etching in the prior art is omitted, meanwhile, the chirality and the change and damage of the structure of the carbon nano tube caused by removing the template and other reagents by a subsequent chemical method are eliminated, and the carbon nano tube ring which is coiled by the single defect-free carbon nano tube, has high density, consistent chirality and perfect structure is obtained.
2. The carbon nano tube ring prepared by the invention has adjustable size, and the average curvature radius distribution of the carbon nano tube ring is adjusted by changing the diameter of a color spot formed by fog drops, so that direct nano-scale characterization and operation are convenient to carry out. The carbon nano tube ring with the controllable curvature radius has potential research value in microscopic physical fields such as nano coils and the like, and provides a new platform for researching the basic physical characteristics of a single carbon nano tube.
3. The invention utilizes a physical method to prepare the carbon nanotube ring from the carbon nanotube, avoids the deformation problem in the preparation process, realizes the lossless separation of the carbon nanotubes with different chiral structures while preparing the carbon nanotube in situ, and obtains the carbon nanotube with high purity, high density and specific topological structure. The preparation method has the advantages of compact connection of the front and rear steps, reasonable design, simplicity and feasibility, all related materials can be purchased from the market, the environment is protected, no pollution is caused, and the carbon nanotube ring with the same chirality, no structural defect and adjustable size can be finally prepared.
4. The carbon nano tube ring provided by the invention is formed by coiling a single carbon nano tube, and the size can be accurately regulated and controlled from a nano level to a micron level. The size of the single carbon nanotube is increased after the single carbon nanotube is wound into a ring, the formed carbon nanotube ring is orderly wound, the number of winding turns is more than 30 circles, and compared with the density of the carbon nanotube in the prior art, the carbon nanotube ring completely belongs to a high-density product and is convenient for optical representation and operation. The carbon nano tube ring is characterized by Raman spectrum, which proves that the carbon nano tube ring has a structure with consistent chirality, and the method for characterizing the Raman spectrum can rapidly and accurately distinguish carbon nano tubes with different chiralities and screen metallic and semiconducting carbon nano tubes, so that the characterization result has high accuracy and a better platform is provided for basic theoretical research of a single carbon nano tube.
Drawings
FIG. 1 is a schematic view of an apparatus for the production process of the present invention;
FIG. 2 is a SEM representation result of a single-ring carbon nanotube ring prepared in example 2 of the present invention;
FIGS. 3a and 3b are TEM characterization results of carbon nanotube rings obtained in example 2 of the present invention at different magnifications;
FIG. 4 is a ring diameter distribution histogram of carbon nanotube rings of different shapes prepared in example 2 of the present invention;
fig. 5a and 5b are raman peak data images of different ranges of raman shifts of a carbon nanotube ring obtained in example 2 of the present invention;
FIG. 6 is a SEM characterization of a bicyclic carbon nanotube ring prepared in example 6 of the present invention;
wherein: 1-high temperature tube furnace, 2-quartz boat, 3-carbon nano tube, 4-DC power supply, 5-electrode plate, 6-fog drop, a-air inlet, b-low temperature zone, c-constant temperature zone.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
The preparation method of the carbon nano tube comprises the following steps:
as shown in FIG. 1, a high-temperature tube furnace capable of setting different reaction temperature regions was used as a reaction apparatus.
1) Mixing ferrocene and sublimed sulfur powder with the molar ratio of 16;
2) Introducing argon of 200sccm into the reactor as protective gas from an air inlet a close to the low-temperature region, and exhausting the air in the reactor to keep an inert environment in the high-temperature tubular furnace; heating a constant temperature area c positioned at the downstream of the high-temperature tubular furnace gas, and introducing 800-1500sccm argon gas and 1-10sccm methane gas when the temperature is raised to 1050-1200 ℃;
3) After the airflow is stable, the low-temperature area is heated to the sublimation temperature of 60-90 ℃, so that the catalyst precursor and the growth promoter are decomposed to form the catalyst, then the catalyst enters the constant-temperature area of the reaction device along with the carrier gas, methane is catalytically cracked in the constant-temperature area, and the carbon nano tubes 3 are grown, most of the products are carbon nano tube bundle aggregates at the time, and the generated carbon nano tubes flow out along with the carrier gas in the outlet direction in the form of aerogel.
The parameters and properties of the prepared carbon nanotubes are shown in table 1.
TABLE 1 preparation parameters and Property parameters of carbon nanotubes
Figure BDA0003343457780000061
Example 2
A) Sample 1 carbon nanotubes were prepared using the method of example 1;
b) An electric field is applied to the tail end of the gas downstream of the high-temperature tube furnace and is introduced by a high-voltage direct-current power supply 4, a plate electrode is vertically placed at the gas outlet end of the high-temperature tube furnace, field intensity is formed from a gas outlet section to the plate electrode area, the electric field intensity is controlled by changing the distance from the gas outlet end to the plane of the plate electrode, and the device is built as shown in figure 1. Adjusting the output voltage of a high-voltage direct-current power supply to be 10kV, controlling the distance between the electrode plate and the tail end of the gas outlet of the high-temperature tube furnace to be 10cm, and controlling the electric field intensity from the gas outlet of the high-temperature tube furnace to the electrode plate to be 100kV/m; under the action of airflow guidance, the carbon nano tubes or tube bundles flying out from the air outlet of the high-temperature tube furnace are charged under the action of an external electric field and are separated under the action of coulomb to obtain single carbon nano tubes;
c) Meanwhile, spraying water mist in the electric field range at the tail end of the air outlet of the high-temperature tube furnace by using a humidifier, wherein the mist amount is controlled to be 200mL/h, and the size of a color spot formed by droplets is 0.17mm; and (3) spontaneously coiling the flying single carbon nano tube under the surface tension action of the fog drops, fishing the fog drops by using a clean silicon wafer, and obtaining a carbon nano tube ring on the silicon wafer.
The prepared carbon nanotube ring is characterized by a scanning electron microscope, and the detection result is shown in fig. 2, wherein the carbon nanotube ring is a nearly circular single-ring carbon nanotube ring with the average curvature radius of 300nm.
The prepared carbon nanotube ring was characterized by using a transmission electron microscope, and the detection results are shown in fig. 3a and 3b, the carbon nanotube ring was formed by crimping a single carbon nanotube, the diameter of the carbon nanotube was 2nm, which was matched with the results of fig. 2, and it was further confirmed that the average radius of curvature of the carbon nanotube ring was 300nm.
The approximate distribution of the ring diameters of the carbon nanotube rings was counted by means of artificial statistics, and the result is shown in fig. 4, where the radius of curvature of the prepared carbon nanotube was between 300 and 500nm, and the average radius of curvature was 300nm.
The characteristic peak of the carbon nano tube in the Raman spectrum is 1500-1600cm -1 Called G peak, and the displacement is 1200-1400cm -1 The characteristic peak of (2) is called D peak, and the ratio of the D peak to the G peak is generally used to reflect the structural defect degree of the carbon nanotube. As shown in FIG. 5a, the carbon nanotube ring is located at 1200-1400cm -1 The D peak is extremely low, which indicates that the prepared carbon nano tube has a perfect ring structure. On the other hand, the general peak shape of the G peak indicates the metallic and semiconducting properties of the carbon nanotube, the G peak of the semiconducting carbon nanotube is sharp and Lorentz, while the G peak of the metallic carbon nanotube is broadened to a BWF peak, and it can be judged from FIG. 5a that the ring of the carbon nanotube thus produced is semiconducting.
The preparation method can obtain the carbon nano tube with the specific structure, high chiral purity, high density and no structural defects in one step without using a chemical reagent as a template, and the single chiral selectivity can reach 100 percent and the purity is 100 percent.
The prepared carbon nanotube ring is free of defects, consistent in chirality and adjustable in size, nanoscale representation and operation are facilitated, the carbon nanotube ring is expected to play an important role in the field of research of basic physical characteristics of carbon nanotubes, and meanwhile, the carbon nanotube ring has great application potential in the fields of micro-nano electronic devices, electromagnetic induction devices, photoelectric devices and the like.
Example 3
A) Sample 2 carbon nanotubes were prepared using the method of example 1;
b) An electric field is added at the tail end of the reactor and is introduced by a high-voltage direct-current power supply, and the device is built as shown in figure 1. And adjusting the output voltage of the high-voltage direct-current power supply to be 12kV, adjusting the distance between the electrode plate and the tail end of the gas outlet of the high-temperature tube furnace to be 10cm, and controlling the electric field intensity from the tail end of the gas outlet of the high-temperature tube furnace to the electrode plate to be 120kV/m. The carbon nano tubes or tube bundles flying out under the guiding action of the airflow are charged and separated under the action of coulomb to obtain single carbon nano tubes;
c) Spraying water mist in the electric field range at the tail end of the air outlet of the high-temperature tubular furnace by using a humidifier, wherein the mist amount is controlled to be 200mL/h, and the size of a color spot formed by the mist drops is 0.17mm. And fishing and connecting the fog drops by using a clean silicon wafer to obtain a single-ring carbon nanotube ring, wherein the curvature radius of the single-ring carbon nanotube ring is between 300 and 500nm, and the average curvature radius of the single-ring carbon nanotube ring is 300nm.
Example 4
A) Sample 3 carbon nanotubes were prepared using the method of example 1;
b) An electric field is added at the tail end of the reactor, the electric field is introduced by a high-voltage direct-current power supply, and the device is built as shown in figure 1. Adjusting the output voltage of the high-voltage direct-current power supply to be 10kV, controlling the distance between the electrode plate and the tail end of the gas outlet of the high-temperature tube furnace to be 10cm, and controlling the electric field intensity from the tail end of the gas outlet of the high-temperature tube furnace to the electrode plate to be 100kV/m. The carbon nano-tubes or tube bundles flying out under the guiding action of the airflow are charged and separated under the action of coulomb to obtain single carbon nano-tubes;
c) Suspending fog drops in an electric field range at the tail end of an air outlet of the high-temperature tubular furnace by using an ultrasonic suspension device, wherein the fog amount is controlled to be 200mL/h, the size of the fog drops can be controlled by the size of a syringe needle, and the size of color spots formed by the fog drops is 0.5mm; and fishing the fog drops by using a clean silicon wafer to obtain a monocyclic carbon nanotube ring, wherein the curvature radius of the monocyclic carbon nanotube ring is between 400 and 700mm, and the average curvature radius is about 600mm.
The prepared carbon nanotube ring was characterized by raman spectroscopy, and the detection result is shown in fig. 5 b. RBM Peak through carbon nanotubes (100-300 cm) -1 ) The diameter and chirality of the carbon nanotube are identified, and the RBM peak positions at different positions on the carbon nanotube ring are the same, so that the carbon nanotube ring has a consistent chiral structure.
Example 5
A) Sample 4 carbon nanotubes were prepared using the method of example 1;
b) An electric field is added at the tail end of the reactor, the electric field is introduced by a high-voltage direct-current power supply, and the device is built as shown in figure 1. Adjusting the output voltage of the high-voltage direct-current power supply to be 12kV, controlling the distance between the electrode plate and the tail end of the gas outlet of the high-temperature tube furnace to be 10cm, and controlling the electric field intensity from the tail end of the gas outlet of the high-temperature tube furnace to the electrode plate to be 120kV/m. The carbon nano tubes or tube bundles flying out under the guiding action of the airflow are charged and separated under the action of coulomb to obtain single carbon nano tubes;
c) And (3) suspending the fog drops in an electric field range at the tail end of the air outlet of the high-temperature tubular furnace by using an ultrasonic suspension device, wherein the fog amount is controlled to be 200mL/h, the size of the fog drops can be controlled by the size of a syringe needle, and the size of a color spot formed by the fog drops is 1mm. And fishing the fog drops by using a clean silicon wafer to obtain a single-ring carbon nanotube ring, wherein the curvature radius of the single-ring carbon nanotube ring is between 0.8 and 1.1 mu m, and the average curvature radius is about 1 mu m.
From the comparison of examples 2-5, the key factor affecting the radius of curvature of the carbon nanotubes is the size of the droplets.
Example 6
A) Sample 2 carbon nanotubes were prepared using the method of example 1;
b) An electric field is added at the tail end of the reactor, the electric field is introduced by a high-voltage direct-current power supply, and the device is built as shown in figure 1. Adjusting the output voltage of the high-voltage direct-current power supply to be 10kV, controlling the distance between the electrode plate and the tail end of the gas outlet of the high-temperature tube furnace to be 10cm, and controlling the electric field intensity from the tail end of the gas outlet of the high-temperature tube furnace to the electrode plate to be 100kV/m. The carbon nano tubes or tube bundles flying out under the guiding action of the airflow are charged and separated under the action of coulomb to obtain single carbon nano tubes;
c) And spraying water mist to the electric field range at the tail end of the air outlet of the high-temperature tube furnace by using the humidifier, wherein the mist quantity of the humidifier is reduced from 200mL/h to 100mL/h. And fishing the fogdrop by using a clean silicon wafer, wherein the size of a color spot formed by the fogdrop is still 0.17mm. And fishing the fog drops by using a clean silicon wafer, and characterizing the prepared carbon nanotube ring by using a scanning electron microscope, wherein the detection result is shown in fig. 6, and the curvature radiuses of the carbon nanotube ring are respectively 140nm and 240nm of the 8-shaped carbon nanotube ring. A possible reason for this is that at low mist levels, the humidity of the air surrounding the mist is relatively low and the mist evaporates quickly. Due to the lack of spherical water drop templates, a small number of pre-formed circular carbon tube rings are distorted and deformed due to strong van der waals effect, and then are converted into 8-shaped structures.
The invention provides a brand new method for preparing an isotactic chiral carbon nanotube ring, which utilizes an external field and the surface tension of fog drops to quickly separate and assemble grown carbon nanotubes into the carbon nanotube ring. The preparation method provided by the invention is simple, can realize synchronous lossless separation of different chiral carbon nanotubes, and has the chiral purity of 100%. The obtained carbon nano tube has perfect ring structure and consistent chiral structure, and the curvature radius can be regulated and controlled by the size of the fogdrop. The carbon nano tube ring prepared by the invention is convenient for nano-scale representation and operation, and provides a new platform for researching the basic physical characteristics of a single carbon nano tube. In addition, the special structure and the homochirality of the carbon nanotube ring bring unique performance, and the carbon nanotube ring has great potential in the field of microscopic physical characteristic research and the application fields of micro-nano electronic devices, electromagnetic induction devices, photoelectric devices and the like.

Claims (10)

1. A preparation method of a carbon nanotube ring is characterized by comprising the following steps:
a) Sublimating the catalyst in an inert environment, and then heating and reacting the catalyst with mixed reaction gas of a carbon source and carrier gas to prepare a carbon nano tube; the specific process is as follows:
1) Mixing a catalyst precursor and a growth promoter in a container, and then placing the container in a low-temperature region at the upstream of the gas of the reaction device;
the catalyst precursor comprises one or more of volatile metal organic compounds;
the growth promoter comprises one or more of sulfur-containing substances;
2) Introducing carrier gas to keep an inert environment in the reaction device, removing impurity gas, heating a constant temperature region at the downstream of the reaction device, adjusting the flow of the carrier gas, and introducing a carbon source; the carbon source comprises a hydrocarbon gas; heating to 800-1200 ℃ in a constant temperature area;
3) Heating the low-temperature area to the sublimation temperature of 60-90 ℃ to decompose the catalyst precursor and the growth promoter to form catalyst particles, then feeding the catalyst particles into a constant-temperature area of a reaction device along with carrier gas to react to obtain carbon nanotubes, allowing the generated carbon nanotubes to flow out of the constant-temperature area along with the carrier gas in an aerogel form, and collecting the carbon nanotubes at an outlet;
b) The carbon nano tube is carried to the gas outlet of the reactor by carrier gas, and an external field is applied to the gas outlet end, so that the carbon nano tube is separated under the induction of external field force;
c) And spraying fog drops into an external field area at the gas outlet end of the reactor, and collecting the fog drops through the substrate to obtain the carbon nanotube ring.
2. The method according to claim 1, wherein in step B), the external field is any one of an electric field, a magnetic field, and an optical field;
the field strength of the fog drop area is controlled to be between 50 and 200 kV/m.
3. The preparation method of claim 1, wherein the average radius of curvature distribution of the carbon nanotube ring is adjusted by changing the diameter of a color spot formed by the droplets, the diameter of the color spot of the droplets is between 0.1 and 2mm, and the average radius of curvature distribution of the corresponding carbon nanotube ring is 50nm to 2 μm.
4. The method according to claim 3,
controlling the diameter of a color spot formed by the fog drops to be 0.17mm to obtain the average curvature radius distribution of the carbon nanotube ring to be 300-500nm;
controlling the diameter of a color spot formed by the fogdrop to be 0.5mm to obtain the average curvature radius distribution of the carbon nano tube ring to be 400-700 nm;
the diameter of the color spot formed by the fogdrop is controlled to be 1mm, and the average curvature radius distribution of the carbon nano tube ring is 0.8-1.1 μm.
5. The preparation method of claim 1, wherein in the step C), the fog drops are one of water drops, oil drops, ethanol drops and acetone drops; obtaining a single-ring carbon nanotube ring by controlling the mist quantity to be 200-300 mL/h; the fog amount is less than 200mL/h, and a polycyclic carbon nano tube ring is obtained;
the substrate comprises a solid substrate and a liquid substrate; the solid substrate comprises any one of a silicon wafer, quartz, gold foil and copper foil; the liquid substrate comprises any one of water, ethanol, ethylene glycol and polyethylene glycol.
6. The carbon nanotube ring obtained by the preparation method of any one of claims 1 to 5, wherein the carbon nanotube ring is formed by overlapping and coiling a single carbon nanotube with the diameter of 0.4 to 10nm, the number of the tube walls of 1 to 5, the length of more than 10 μm and a perfect structure, and the average curvature radius of the carbon nanotube ring is 50nm to 2 μm.
7. The carbon nanotube ring according to claim 6, wherein the carbon nanotube ring has a single chiral structure, and has a chiral selectivity of 100% and a purity of 100%.
8. The carbon nanotube ring of claim 6, wherein the single carbon nanotube has a diameter of 0.7-4nm and a length >30 μm.
9. The carbon nanotube ring according to claim 6, wherein the carbon nanotube ring is one or more than two rings formed by overlapping and winding a single carbon nanotube.
10. The use of the carbon nanotube ring of any one of claims 6 to 9, wherein the carbon nanotube ring has a doubled scattering cross-section after the carbon nanotubes are overlapped and coiled, and is used for optical measurement and characterization of the single carbon nanotube.
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